CN115006606A - A kind of hydrophilic lubricating coating and preparation method and application thereof - Google Patents
A kind of hydrophilic lubricating coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN115006606A CN115006606A CN202210164285.7A CN202210164285A CN115006606A CN 115006606 A CN115006606 A CN 115006606A CN 202210164285 A CN202210164285 A CN 202210164285A CN 115006606 A CN115006606 A CN 115006606A
- Authority
- CN
- China
- Prior art keywords
- monomer
- preparation
- adhesive
- hydrophilic
- lubricating coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 74
- 239000011248 coating agent Substances 0.000 title claims abstract description 66
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 86
- 230000001070 adhesive effect Effects 0.000 claims description 67
- 239000000853 adhesive Substances 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 24
- 229920006037 cross link polymer Polymers 0.000 claims description 23
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052794 bromium Inorganic materials 0.000 claims description 19
- 125000005907 alkyl ester group Chemical group 0.000 claims description 17
- 230000002209 hydrophobic effect Effects 0.000 claims description 17
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 9
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 9
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims description 9
- NQIMONOHVBBZKE-UHFFFAOYSA-N n-[2-(3,4-dihydroxyphenyl)ethyl]-2-methylprop-2-enamide Chemical group CC(=C)C(=O)NCCC1=CC=C(O)C(O)=C1 NQIMONOHVBBZKE-UHFFFAOYSA-N 0.000 claims description 8
- -1 methacryloyloxyethyl Chemical group 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- TXNUHSYBHYPDFT-UHFFFAOYSA-N butyl 2-ethoxyprop-2-enoate Chemical compound CCCCOC(=O)C(=C)OCC TXNUHSYBHYPDFT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- CTTOYDHUFQNBDZ-UHFFFAOYSA-N ethyl 2-methoxyprop-2-enoate Chemical compound CCOC(=O)C(=C)OC CTTOYDHUFQNBDZ-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012429 reaction media Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Chemical group 0.000 claims description 4
- 229910052739 hydrogen Chemical group 0.000 claims description 4
- 229940117986 sulfobetaine Drugs 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- QJYYJRJVWBOLJZ-UHFFFAOYSA-N butyl 2-methoxyprop-2-enoate Chemical compound CCCCOC(=O)C(=C)OC QJYYJRJVWBOLJZ-UHFFFAOYSA-N 0.000 claims description 3
- WXMSGMOIAQWILS-UHFFFAOYSA-N ethyl 2-ethoxyprop-2-enoate Chemical compound CCOC(=C)C(=O)OCC WXMSGMOIAQWILS-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- LFJDOCORGNULHD-UHFFFAOYSA-N propyl 2-methoxyprop-2-enoate Chemical compound CCCOC(=O)C(=C)OC LFJDOCORGNULHD-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- ZSSFHHYKJOKKJM-UHFFFAOYSA-N propyl 2-ethoxyprop-2-enoate Chemical compound CCCOC(=O)C(=C)OCC ZSSFHHYKJOKKJM-UHFFFAOYSA-N 0.000 claims description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 5
- 239000008367 deionised water Substances 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000007853 buffer solution Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 32
- 229910001069 Ti alloy Inorganic materials 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002609 medium Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000002579 anti-swelling effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 3
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- PNOXUQIZPBURMT-UHFFFAOYSA-M potassium;3-(2-methylprop-2-enoyloxy)propane-1-sulfonate Chemical compound [K+].CC(=C)C(=O)OCCCS([O-])(=O)=O PNOXUQIZPBURMT-UHFFFAOYSA-M 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 241000309551 Arthraxon hispidus Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BTTXESIFAHCXMK-UHFFFAOYSA-N methyl 2-methoxyprop-2-enoate Chemical compound COC(=C)C(=O)OC BTTXESIFAHCXMK-UHFFFAOYSA-N 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ICNCZFQYZKPYMS-UHFFFAOYSA-N 2-methylpropanoyl bromide Chemical class CC(C)C(Br)=O ICNCZFQYZKPYMS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RBVLUTAXWVILBT-UHFFFAOYSA-N ethyl prop-2-eneperoxoate Chemical compound CCOOC(=O)C=C RBVLUTAXWVILBT-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZQUDHVGNIZTEDK-UHFFFAOYSA-M potassium;propane-1-sulfonate Chemical compound [K+].CCCS([O-])(=O)=O ZQUDHVGNIZTEDK-UHFFFAOYSA-M 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/10—Materials for lubricating medical devices
Landscapes
- Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
技术领域technical field
本发明涉及材料表面改性技术领域,尤其涉及一种亲水润滑涂层及其制备方法和应用。The invention relates to the technical field of material surface modification, in particular to a hydrophilic lubricating coating and a preparation method and application thereof.
背景技术Background technique
对于介入型医疗器件(如医用导管),为了顺利到达病变点进行诊断和治疗,其应该具有以下特征:表面具有优良的润滑性能,否则会对人体造成刮伤;具有很好的生物相容性,避免引起炎症等二次伤害。For interventional medical devices (such as medical catheters), in order to successfully reach the lesion for diagnosis and treatment, it should have the following characteristics: the surface has excellent lubricating properties, otherwise it will cause scratches to the human body; it has good biocompatibility , to avoid secondary damage such as inflammation.
目前,提高介入型导管水润滑性能的方法主要有两种:一种方法是在传统本体导管外壁涂覆润滑液。如US 5620738A中公开了在本体导管表面涂覆修饰聚乙烯吡咯烷酮(PVP)亲水润滑涂层的技术,尽管修饰后导管具有很好的润滑性,然而PVP涂层与基材之间往往是通过非化学键交联,使得PVP在吸水膨胀后很容易脱落,进而导致导管表面失去亲水润滑作用。At present, there are two main methods to improve the water lubricating performance of the interventional catheter: one method is to coat the outer wall of the traditional body catheter with lubricating fluid. For example, US 5620738A discloses the technology of coating modified polyvinylpyrrolidone (PVP) hydrophilic lubricating coating on the surface of the body catheter. Although the modified catheter has good lubricity, the PVP coating and the substrate often pass through The non-chemical cross-linking makes PVP easy to fall off after swelling by water absorption, which leads to the loss of hydrophilic lubrication on the surface of the catheter.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种亲水润滑涂层及其制备方法和应用。本发明制得的亲水润滑涂层的界面。The purpose of the present invention is to provide a hydrophilic lubricating coating and its preparation method and application. The interface of the hydrophilic lubricating coating prepared by the present invention.
为了实现上述发明目的,本发明提供以下技术方案:In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种亲水润滑涂层的制备方法,包括以下步骤:The invention provides a preparation method of a hydrophilic lubricating coating, comprising the following steps:
将亲水性丙烯酸基单体、疏水性烷基酯单体、黏附性单体、含溴引发剂单体、引发剂和反应介质混合进行自由基聚合反应,得到黏附性共聚物;所述黏附性单体为多巴胺甲基丙烯酰胺;The hydrophilic acrylic monomer, the hydrophobic alkyl ester monomer, the adhesive monomer, the bromine-containing initiator monomer, the initiator and the reaction medium are mixed for free radical polymerization to obtain an adhesive copolymer; the adhesive The sex monomer is dopamine methacrylamide;
将所述黏附性共聚物、固化交联剂和溶剂介质混合进行固化,得到交联型聚合物黏附活性层;Mixing the adhesive copolymer, the curing crosslinking agent and the solvent medium for curing to obtain a crosslinked polymer adhesive active layer;
在保护气氛下,将所述交联型聚合物黏附活性层浸入原子转移自由基聚合反应溶液中进行聚合反应,形成聚合物-聚电解质刷复合层,得到所述亲水润滑涂层;所述原子转移自由基聚合反应溶液包括反应溶剂、反应单体、2,2-联吡啶和溴化亚铜。Under a protective atmosphere, the cross-linked polymer adhesive active layer is immersed in an atom transfer radical polymerization reaction solution to carry out a polymerization reaction to form a polymer-polyelectrolyte brush composite layer to obtain the hydrophilic lubricating coating; the The atom transfer radical polymerization reaction solution includes a reaction solvent, a reaction monomer, 2,2-bipyridine and cuprous bromide.
优选地,所述亲水性丙烯酸基单体、黏附性单体和疏水性烷基酯单体的质量比为1:1:10~1:4:25。Preferably, the mass ratio of the hydrophilic acrylic monomer, the adhesive monomer and the hydrophobic alkyl ester monomer is 1:1:10˜1:4:25.
优选地,所述含溴引发剂单体的用量为亲水性丙烯酸基单体、黏附性单体和疏水性烷基酯单体总质量的1%~5%。Preferably, the amount of the bromine-containing initiator monomer is 1% to 5% of the total mass of the hydrophilic acrylic monomer, the adhesive monomer and the hydrophobic alkyl ester monomer.
优选地,所述亲水性丙烯酸基单体包括丙烯酸、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯和甲基丙烯酸羟丁酯中的一种或多种。Preferably, the hydrophilic acrylic-based monomer includes one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate.
优选地,所述疏水性烷基酯单体包括甲氧基丙烯酸乙酯、甲氧基丙烯酸丙酯、甲氧基丙烯酸丁酯、甲氧基丙烯酸甲酯、乙氧基丙烯酸乙酯、乙氧基丙烯酸丙酯和乙氧基丙烯酸丁酯中的一种或多种。Preferably, the hydrophobic alkyl ester monomer includes ethyl methoxyacrylate, propyl methoxyacrylate, butyl methoxyacrylate, methyl methoxyacrylate, ethyl ethoxyacrylate, ethoxyacrylate One or more of propyl acrylate and butyl ethoxyacrylate.
优选地,所述含溴引发剂单体的结构式如式I所示:Preferably, the structural formula of the bromine-containing initiator monomer is shown in formula I:
式I中,R为甲基或氢,n为1、2或3。In formula I, R is methyl or hydrogen, and n is 1, 2 or 3.
优选地,所述固化交联剂为1,6-己二异氰酸酯、二苯基甲烷二异氰酸酯或甲苯二异氰酸酯。Preferably, the curing crosslinking agent is 1,6-hexamethylene diisocyanate, diphenylmethane diisocyanate or toluene diisocyanate.
优选地,所述反应单体包括甲基丙烯酸3-磺酸丙酯钾盐、磺基甜菜碱甲基丙烯酸酯、甲基丙烯酰氧乙基三甲基氯化铵、甲基丙烯酸钠、甲基丙烯酸羟乙酯和2-甲基丙烯酰氧乙基磷脂酰胆碱中的一种或多种。Preferably, the reaction monomers include potassium 3-sulfopropyl methacrylate, sulfobetaine methacrylate, methacryloyloxyethyltrimethylammonium chloride, sodium methacrylate, methyl methacrylate One or more of hydroxyethyl acrylate and 2-methacryloyloxyethylphosphatidylcholine.
本发明还提供了上述技术方案所述的制备方法制得的亲水润滑涂层,其特征在于,包括交联型聚合物黏附活性层和聚合物-聚电解质刷复合层。The present invention also provides the hydrophilic lubricating coating prepared by the preparation method described in the above technical solution, which is characterized by comprising a cross-linked polymer adhesive active layer and a polymer-polyelectrolyte brush composite layer.
本发明还提供了上述技术方案所述的亲水润滑涂层在表面工程和生物医疗器械改性领域中的应用。The present invention also provides the application of the hydrophilic lubricating coating described in the above technical solution in the fields of surface engineering and biomedical device modification.
本发明提供了一种亲水润滑涂层的制备方法,包括以下步骤:将亲水性丙烯酸基单体、疏水性烷基酯单体、黏附性单体、含溴引发剂单体、引发剂和反应介质混合进行自由基聚合反应,得到黏附性共聚物;所述黏附性单体为多巴胺甲基丙烯酰胺;将所述黏附性共聚物、固化交联剂和溶剂介质混合进行固化,得到交联型聚合物黏附活性层;在保护气氛下,将所述交联型聚合物黏附活性层浸入原子转移自由基聚合(ATRP)反应溶液中进行聚合反应,形成聚合物-聚电解质刷复合层,得到所述亲水润滑涂层;所述原子转移自由基聚合反应溶液包括反应溶剂、反应单体、2,2-联吡啶和溴化亚铜。The invention provides a preparation method of a hydrophilic lubricating coating, which comprises the following steps: mixing a hydrophilic acrylic monomer, a hydrophobic alkyl ester monomer, an adhesive monomer, a bromine-containing initiator monomer, and an initiator Mixing with a reaction medium to carry out a free radical polymerization reaction to obtain an adhesive copolymer; the adhesive monomer is dopamine methacrylamide; mixing the adhesive copolymer, a curing crosslinking agent and a solvent medium for curing to obtain a crosslinking A linked polymer adhesive active layer; under a protective atmosphere, the crosslinked polymer adhesive active layer is immersed in an atom transfer radical polymerization (ATRP) reaction solution to carry out a polymerization reaction to form a polymer-polyelectrolyte brush composite layer, The hydrophilic lubricating coating is obtained; the atom transfer radical polymerization reaction solution includes a reaction solvent, a reaction monomer, 2,2-bipyridine and cuprous bromide.
本发明提供的亲水润滑涂层在水介质中具有优异的界面粘接及抗溶胀稳定性能,且在高载荷下具有低摩擦系数,优异的界面粘接及抗溶胀稳定性能取决于交联型聚合物黏附活性层在基材表面优异的界面键合能力和抗介质溶胀性能;高载荷下具有低摩擦系数取决于表面聚合物-聚电解质刷复合层优异的水化特性,具体解释如下:1.界面粘接:黏附性单体内多巴胺分子上的儿茶酚官能团能够与不同的基底材料形成氢键、共价键或金属配位键,含有羟基的亲水性丙烯酸基单体在固化交联剂的作用下交联形成化学网络,在这两方面的共同作用下使得聚合物黏附活性层与基底紧密粘合;2.抗溶胀:合成的黏附性单体结构中含有大量疏水性烷基酯分子,因此在液体中抗溶胀性能较好;3.低摩擦系数:通过ATRP反应在黏附活性层表面接枝亲水性聚合物刷后,聚合物刷与水分子之间存在强相互作用,形成稳定的水化层,水化层中的水分子可以自由流动,能够适应剪切力的作用,降低了摩擦系数。The hydrophilic lubricating coating provided by the present invention has excellent interfacial adhesion and anti-swelling stability in aqueous medium, and has low friction coefficient under high load, and the excellent interfacial adhesion and anti-swelling stability depend on the cross-linking type The excellent interfacial bonding ability and anti-swelling performance of the polymer adhesive active layer on the substrate surface; the low coefficient of friction under high load depends on the excellent hydration properties of the surface polymer-polyelectrolyte brush composite layer, which are explained as follows: 1 .Interface bonding: The catechol functional group on the dopamine molecule in the adhesive monomer can form hydrogen bonds, covalent bonds or metal coordination bonds with different substrate materials, and the hydrophilic acrylic monomers containing hydroxyl groups can be cured and crosslinked. Under the action of the agent, cross-linking forms a chemical network, and under the combined action of these two aspects, the polymer adhesive active layer is closely bonded to the substrate; 2. Anti-swelling: The synthesized adhesive monomer structure contains a large amount of hydrophobic alkyl esters 3. Low coefficient of friction: After grafting the hydrophilic polymer brush on the surface of the adhesive active layer through the ATRP reaction, there is a strong interaction between the polymer brush and water molecules, forming Stable hydration layer, water molecules in the hydration layer can flow freely, can adapt to the action of shear force, and reduce the coefficient of friction.
本发明具有的有益效果:The beneficial effects that the present invention has:
(1)修饰方法几乎适用于所有基材和医疗器械表面;(2)制备得到的亲水润滑涂层与基材结合力强、力学性能优异;(3)亲水润滑涂层具有优异的抗溶胀和介质稳定性;(4)亲水润滑涂层具有低摩擦和高承载特性;(5)亲水润滑涂层制备方法简单、基材通用性强。(1) The modification method is suitable for almost all substrates and surfaces of medical devices; (2) The prepared hydrophilic lubricating coating has strong adhesion to the substrate and excellent mechanical properties; (3) The hydrophilic lubricating coating has excellent resistance to Swelling and medium stability; (4) the hydrophilic lubricating coating has low friction and high load-bearing properties; (5) the hydrophilic lubricating coating has a simple preparation method and strong substrate versatility.
实施例的数据表明,本发明制得的亲水润滑涂层与基材之间的黏附强度为1.5MPa,力学模量为10MPa;耐水性强,可在去离子水、缓冲液和生理盐水等介质中保持长期粘接稳定性;以聚二甲基硅氧烷球为对偶,在10N载荷下,去离子水作为润滑剂,涂层表面摩擦系数为0.02;所制备的亲水润滑涂层稳定性和润滑性能优异,有望在表面工程和生物医疗器械领域被广泛应用。The data of the examples show that the adhesion strength between the hydrophilic lubricating coating prepared by the present invention and the substrate is 1.5 MPa, and the mechanical modulus is 10 MPa; Long-term adhesion stability is maintained in the medium; with polydimethylsiloxane spheres as a pair, deionized water is used as a lubricant under a load of 10N, and the surface friction coefficient of the coating is 0.02; the prepared hydrophilic lubricating coating is stable It has excellent properties and lubricating properties, and is expected to be widely used in the fields of surface engineering and biomedical devices.
附图说明Description of drawings
图1为基材表面制备得到亲水润滑涂层的结构示意图;1 is a schematic structural diagram of a hydrophilic lubricating coating prepared on the surface of a substrate;
图2为钛合金基材表面制备得到亲水润滑涂层的扫描电子显微镜断面图;Fig. 2 is a scanning electron microscope cross-sectional view of a hydrophilic lubricating coating prepared on the surface of a titanium alloy substrate;
图3为钛合金基材表面制备得到亲水润滑涂层与钛合金基材界面黏附强度测试曲线图;Fig. 3 is a test curve of the adhesion strength of the interface between the hydrophilic lubricating coating prepared on the surface of the titanium alloy substrate and the titanium alloy substrate;
图4为钛合金基材表面制备得到亲水润滑涂层的摩擦系数测试结果图;Fig. 4 is the test result diagram of the friction coefficient of the hydrophilic lubricating coating prepared on the surface of the titanium alloy substrate;
图5为钛合金基材表面制备得到亲水润滑涂层在水、PBS缓冲液和生理盐水中的稳定性评价;Figure 5 shows the stability evaluation of the hydrophilic lubricating coating prepared on the surface of the titanium alloy substrate in water, PBS buffer and physiological saline;
图6为不同基材表面制备得到亲水润滑涂层的摩擦系数测试结果图;Fig. 6 is the test result diagram of the friction coefficient of the hydrophilic lubricating coating prepared on the surface of different substrates;
图7为此修饰方法在PVC导尿管、口腔气道插管和钛合金人工关节头表面的应用演示。Figure 7 demonstrates the application of this modification method on the surface of PVC catheter, oral airway cannula and titanium alloy artificial joint head.
具体实施方式Detailed ways
本发明提供了一种亲水润滑涂层的制备方法,包括以下步骤:The invention provides a preparation method of a hydrophilic lubricating coating, comprising the following steps:
将亲水性丙烯酸基单体、疏水性烷基酯单体、黏附性单体、含溴引发剂单体、引发剂和反应介质混合进行自由基聚合反应,得到黏附性共聚物;所述黏附性单体为多巴胺甲基丙烯酰胺;The hydrophilic acrylic monomer, the hydrophobic alkyl ester monomer, the adhesive monomer, the bromine-containing initiator monomer, the initiator and the reaction medium are mixed for free radical polymerization to obtain an adhesive copolymer; the adhesive The sex monomer is dopamine methacrylamide;
将所述黏附性共聚物、固化交联剂和溶剂介质混合进行固化,得到交联型聚合物黏附活性层;Mixing the adhesive copolymer, the curing crosslinking agent and the solvent medium for curing to obtain a crosslinked polymer adhesive active layer;
在保护气氛下,将所述交联型聚合物黏附活性层浸入原子转移自由基聚合反应溶液中进行聚合反应,形成聚合物-聚电解质刷复合层,得到所述亲水润滑涂层;所述原子转移自由基聚合反应溶液包括反应溶剂、反应单体、2,2-联吡啶和溴化亚铜。Under a protective atmosphere, the cross-linked polymer adhesive active layer is immersed in an atom transfer radical polymerization reaction solution to carry out a polymerization reaction to form a polymer-polyelectrolyte brush composite layer to obtain the hydrophilic lubricating coating; the The atom transfer radical polymerization reaction solution includes a reaction solvent, a reaction monomer, 2,2-bipyridine and cuprous bromide.
在本发明中,若无特殊说明,使用的原料均为本领域市售商品。In the present invention, unless otherwise specified, the raw materials used are all commercially available products in the field.
本发明将亲水性丙烯酸基单体、疏水性烷基酯单体、黏附性单体、含溴引发剂单体、引发剂和溶剂介质混合进行自由基聚合反应,得到黏附性共聚物;所述黏附性单体为多巴胺甲基丙烯酰胺。In the present invention, the hydrophilic acrylic monomer, the hydrophobic alkyl ester monomer, the adhesive monomer, the bromine-containing initiator monomer, the initiator and the solvent medium are mixed for free radical polymerization to obtain the adhesive copolymer; The adhesive monomer is dopamine methacrylamide.
在本发明中,所述亲水性丙烯酸基单体、黏附性单体和疏水性烷基酯单体的质量比优选为1:1:10~1:4:25。In the present invention, the mass ratio of the hydrophilic acrylic monomer, the adhesive monomer and the hydrophobic alkyl ester monomer is preferably 1:1:10 to 1:4:25.
在本发明中,所述含溴引发剂单体的用量优选为亲水性丙烯酸基单体、黏附性单体和疏水性烷基酯单体总质量的1%~5%,更优选为2%~4%。In the present invention, the dosage of the bromine-containing initiator monomer is preferably 1% to 5% of the total mass of the hydrophilic acrylic monomer, adhesive monomer and hydrophobic alkyl ester monomer, more preferably 2% %~4%.
在本发明中,所述亲水性丙烯酸基单体优选包括丙烯酸、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯和甲基丙烯酸羟丁酯中的一种或多种。In the present invention, the hydrophilic acrylic-based monomer preferably includes one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate.
在本发明中,所述疏水性烷基酯单体优选包括甲氧基丙烯酸乙酯、甲氧基丙烯酸丙酯、甲氧基丙烯酸丁酯、甲氧基丙烯酸甲酯、乙氧基丙烯酸乙酯、乙氧基丙烯酸丙酯和乙氧基丙烯酸丁酯中的一种或多种。In the present invention, the hydrophobic alkyl ester monomer preferably includes ethyl methoxyacrylate, propyl methoxyacrylate, butyl methoxyacrylate, methyl methoxyacrylate, and ethyl ethoxyacrylate , one or more of propyl ethoxyacrylate and butyl ethoxyacrylate.
在本发明中,所述含溴引发剂单体的结构式优选如式I所示:In the present invention, the structural formula of the bromine-containing initiator monomer is preferably as shown in formula I:
式I中,R为甲基或氢,n为1、2或3。In formula I, R is methyl or hydrogen, and n is 1, 2 or 3.
在本发明中,所述含溴引发剂单体优选由包括以下步骤的方法制得:In the present invention, the bromine-containing initiator monomer is preferably prepared by a method comprising the following steps:
将甲基丙烯酸羟酯类单体、三乙胺和二氯甲烷混合,逐滴加入溴代异丁酰溴后,在0℃冰浴和氮气保护气氛下,反应后得到的反应液经过滤、洗涤和旋蒸处理,得到所述含溴引发剂单体。Mix the hydroxy methacrylate monomer, triethylamine and dichloromethane, add bromoisobutyryl bromide dropwise, under 0 ℃ ice bath and nitrogen protective atmosphere, the reaction solution obtained after the reaction is filtered, The bromine-containing initiator monomer is obtained by washing and rotary evaporation.
在本发明中,所述甲基丙烯酸羟酯类单体优选为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯或甲基丙烯酸羟丁酯。In the present invention, the hydroxy methacrylate monomer is preferably hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl methacrylate.
在本发明中,所述甲基丙烯酸羟酯类单体、三乙胺和溴代异丁酰溴的摩尔比优选为2:1:2~2.5。In the present invention, the molar ratio of the hydroxy methacrylate monomer, triethylamine and bromoisobutyryl bromide is preferably 2:1:2-2.5.
在本发明中,所述反应的时间优选为4h。In the present invention, the reaction time is preferably 4h.
本发明对所述过滤、洗涤和旋蒸处理的具体方式没有特殊的限定,采用本领域技术人员熟知的方式即可。The present invention has no particular limitation on the specific methods of the filtration, washing and rotary evaporation, and methods well known to those skilled in the art can be used.
在本发明中,所述洗涤优选使用二氯甲烷。In the present invention, dichloromethane is preferably used for the washing.
所述洗涤完成后,本发明优选将所得滤液依次使用饱和碳酸钠和饱和氯化钠溶液分别洗涤2次,直至溶液pH值达到7。After the washing is completed, in the present invention, the obtained filtrate is preferably washed twice with saturated sodium carbonate and saturated sodium chloride solution successively until the pH value of the solution reaches 7.
在本发明中,所述引发剂优选为偶氮二异丁腈,所述引发剂的用量优选为亲水性丙烯酸基单体、黏附性单体和疏水性烷基酯单体总摩尔量的0.005~2%,进一步优选为0.01~1%,更优选为0.01~0.05%。In the present invention, the initiator is preferably azobisisobutyronitrile, and the amount of the initiator is preferably the total molar amount of the hydrophilic acrylic monomer, the adhesive monomer and the hydrophobic alkyl ester monomer. 0.005 to 2%, more preferably 0.01 to 1%, more preferably 0.01 to 0.05%.
在本发明中,所述反应介质优选为N,N-二甲基甲酰胺,本发明对所述反应介质的用量没有特殊限定,只要能够使单体充分混合即可。In the present invention, the reaction medium is preferably N,N-dimethylformamide, and the amount of the reaction medium is not particularly limited in the present invention, as long as the monomers can be sufficiently mixed.
本发明对所述亲水性丙烯酸基单体、黏附性单体、疏水性烷基酯单体、引发剂、含溴引发剂单体和溶剂介质的加入顺序没有特殊的限定。The present invention has no special limitation on the order of adding the hydrophilic acrylic monomer, adhesive monomer, hydrophobic alkyl ester monomer, initiator, bromine-containing initiator monomer and solvent medium.
在本发明中,所述自由基聚合反应的温度优选为50~80℃,更优选为70~80℃,时间优选为12~24h,进一步优选为15~21h。在本发明中,所述自由基聚合反应优选在保护气氛下进行;所述保护气氛优选为氮气。In the present invention, the temperature of the radical polymerization reaction is preferably 50-80° C., more preferably 70-80° C., and the time is preferably 12-24 h, more preferably 15-21 h. In the present invention, the radical polymerization reaction is preferably carried out under a protective atmosphere; the protective atmosphere is preferably nitrogen.
所述自由基聚合反应结束后,本发明优选将所得自由基聚合反应产物用乙酸乙酯溶解,再用正己烷沉降,去掉上层清液;将沉降物进行烘干,即得到所述黏附性共聚物。After the free radical polymerization reaction is completed, the present invention preferably dissolves the obtained free radical polymerization reaction product with ethyl acetate, then settles with n-hexane, and removes the supernatant; drying the precipitate to obtain the adhesive copolymerization thing.
在本发明中,所述正己烷沉降的时间优选为24h。In the present invention, the time for the n-hexane to settle is preferably 24h.
在本发明中,所述烘干温度优选为60℃,时间优选为24h。在本发明中,所述烘干优选在真空干燥箱中进行。In the present invention, the drying temperature is preferably 60°C, and the time is preferably 24h. In the present invention, the drying is preferably carried out in a vacuum drying oven.
得到黏附性共聚物后,本发明将所述黏附性共聚物、固化交联剂和溶剂介质混合进行固化,得到交联型聚合物黏附活性层。After the adhesive copolymer is obtained, in the present invention, the adhesive copolymer, the curing crosslinking agent and the solvent medium are mixed and cured to obtain a crosslinked polymer adhesive active layer.
在本发明中,所述固化交联剂优选为1,6-己二异氰酸酯、二苯基甲烷二异氰酸酯或甲苯二异氰酸酯。In the present invention, the curing crosslinking agent is preferably 1,6-hexamethylene diisocyanate, diphenylmethane diisocyanate or toluene diisocyanate.
在本发明中,所述固化交联剂的用量优选为亲水性丙烯酸单体质量的10%~60%。In the present invention, the amount of the curing crosslinking agent is preferably 10% to 60% of the mass of the hydrophilic acrylic monomer.
在本发明中,所述溶剂介质优选为二氯甲烷,本发明对所述溶剂介质的用量没有特殊限定,只要能够使聚合物溶解即可。In the present invention, the solvent medium is preferably dichloromethane, and the amount of the solvent medium is not particularly limited in the present invention, as long as the polymer can be dissolved.
在本发明中,所述固化的温度优选为20~60℃,更优选为30~40℃,时间优选为24~96h。In the present invention, the curing temperature is preferably 20-60° C., more preferably 30-40° C., and the time is preferably 24-96 h.
本发明将所述黏附性共聚物、溶剂介质和固化交联剂混合后,涂敷到材料和器械表面,进行所述固化,在材料和器械表面形成所述交联型聚合物黏附活性层。In the present invention, after mixing the adhesive copolymer, solvent medium and curing cross-linking agent, it is coated on the surfaces of materials and devices, and the curing is performed to form the cross-linked polymer adhesive active layer on the surfaces of materials and devices.
得到交联型聚合物黏附活性层后,本发明在保护气氛下,将所述交联型聚合物黏附活性层浸入原子转移自由基聚合反应溶液中进行聚合反应,形成聚合物-聚电解质刷复合层,得到所述亲水润滑涂层;所述原子转移自由基聚合反应溶液包括反应溶剂、反应单体、2,2-联吡啶和溴化亚铜。After the cross-linked polymer adhesive active layer is obtained, in the present invention, the cross-linked polymer adhesive active layer is immersed in an atom transfer radical polymerization reaction solution under a protective atmosphere to carry out a polymerization reaction to form a polymer-polyelectrolyte brush composite layer to obtain the hydrophilic lubricating coating; the atom transfer radical polymerization reaction solution includes a reaction solvent, a reaction monomer, 2,2-bipyridine and cuprous bromide.
在本发明中,所述保护气氛优选为氮气或氩气。In the present invention, the protective atmosphere is preferably nitrogen or argon.
在本发明中,所述反应单体优选为甲基丙烯酸3-磺酸丙酯钾盐、磺基甜菜碱甲基丙烯酸酯、甲基丙烯酰氧乙基三甲基氯化铵、甲基丙烯酸钠、甲基丙烯酸羟乙酯和2-甲基丙烯酰氧乙基磷脂酰胆碱中的一种或多种。In the present invention, the reaction monomer is preferably 3-sulfopropyl methacrylate potassium salt, sulfobetaine methacrylate, methacryloyloxyethyltrimethylammonium chloride, methacrylic acid One or more of sodium, hydroxyethyl methacrylate and 2-methacryloyloxyethylphosphatidylcholine.
在本发明中,所述反应溶剂优选为甲醇和水的混合物,所述混合物中甲醇和水的体积比优选为1:1~1:4,更优选为1:2~1:3。In the present invention, the reaction solvent is preferably a mixture of methanol and water, and the volume ratio of methanol and water in the mixture is preferably 1:1-1:4, more preferably 1:2-1:3.
在本发明中,所述反应单体、2,2-联吡啶和溴化亚铜的摩尔比优选为1:0.01~0.05:0.005~0.02,更优选为1:0.02~0.04:0.01~0.015。In the present invention, the molar ratio of the reaction monomer, 2,2-bipyridine and cuprous bromide is preferably 1:0.01-0.05:0.005-0.02, more preferably 1:0.02-0.04:0.01-0.015.
在本发明中,所述聚合反应温度优选为20~40℃,时间优选为5~20min,更优选为8min;本发明对所述ATRP反应液的配制方法没有特殊要求,将上述原料在在氩气保护下充分搅拌均匀即可。In the present invention, the polymerization reaction temperature is preferably 20-40° C., and the time is preferably 5-20 minutes, more preferably 8 minutes; the present invention has no special requirements for the preparation method of the ATRP reaction solution. Stir well under air protection.
本发明优选在保护气氛下,将表面修饰了交联型聚合物黏附活性层的材料和器械浸到ATRP反应液中进行聚合反应,产生聚合物-聚电解质刷复合层,制备得到双层亲水润滑涂层。In the present invention, preferably under a protective atmosphere, the materials and devices whose surfaces are modified with the cross-linked polymer adhesive active layer are immersed in the ATRP reaction solution to carry out a polymerization reaction to produce a polymer-polyelectrolyte brush composite layer, and a double-layer hydrophilic layer is prepared. Lubrication coating.
本发明还提供了上述技术方案所述的制备方法制得的亲水润滑涂层,其特征在于,包括交联型聚合物黏附活性层和聚合物-聚电解质刷复合层。The present invention also provides the hydrophilic lubricating coating prepared by the preparation method described in the above technical solution, which is characterized by comprising a cross-linked polymer adhesive active layer and a polymer-polyelectrolyte brush composite layer.
图1为基材表面制备得到亲水润滑涂层的结构示意图。Figure 1 is a schematic structural diagram of a hydrophilic lubricating coating prepared on the surface of a substrate.
本发明还提供了上述技术方案所述的亲水润滑涂层在表面工程和生物医疗器械改性领域中的应用。The present invention also provides the application of the hydrophilic lubricating coating described in the above technical solution in the fields of surface engineering and biomedical device modification.
本发明对黏附所述亲水润滑涂层的使用方法不做具体限定,将其涂覆在相应的材料和器械上即可。在本发明中,所述材料和器械优选包括玻璃、铝片、钛片、各种合金、聚二甲基硅氧烷、塑料、陶瓷、动物组织或骨头,以及植介入生物医疗器械,所述植介入生物医疗器械优选包括引流管、插管、支架或植入替换件。The present invention does not specifically limit the use method of adhering the hydrophilic lubricating coating, and it can be coated on corresponding materials and instruments. In the present invention, the materials and devices preferably include glass, aluminum sheets, titanium sheets, various alloys, polydimethylsiloxane, plastics, ceramics, animal tissue or bone, and implanted interventional biomedical devices, the said The implanted interventional biomedical device preferably includes a drain, cannula, stent or implant replacement.
下面将结合本发明中的实施例,对本发明中的技术方案进行清楚、完整地描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
亲水润滑涂层材料的制备和涂覆修饰方法Preparation and coating modification method of hydrophilic lubricating coating material
(1)10.41g甲基丙烯酸羟乙酯和4.10g三乙胺溶于30mL二氯甲烷中,待完全溶解后转移至250mL圆底烧瓶中,0℃冰浴中通氮气20min;23.21g溴代异丁酰溴溶于10mL二氯甲烷中,使用恒压漏斗将其逐滴加入圆底烧瓶中;在0℃冰浴环境下搅拌反应4小时后,将反应物过滤除去白色沉淀,并使用二氯甲烷清洗两次;收集滤液,依次使用饱和碳酸钠和饱和氯化钠溶液分别洗涤滤液2次,直至溶液pH达到7。最后通过旋蒸去除水分和残余溶剂,收集到浅黄色液体即为含溴引发剂单体产物。(1) 10.41g of hydroxyethyl methacrylate and 4.10g of triethylamine were dissolved in 30mL of dichloromethane, transferred to a 250mL round-bottomed flask after complete dissolution, and nitrogen was passed through an ice bath at 0°C for 20min; 23.21g of brominated Isobutyryl bromide was dissolved in 10 mL of dichloromethane, and it was added dropwise to a round-bottomed flask using a constant pressure funnel; after stirring the reaction for 4 hours in an ice bath at 0 °C, the reactant was filtered to remove the white precipitate, and di Chloromethane was washed twice; the filtrate was collected, and the filtrate was washed twice with saturated sodium carbonate and saturated sodium chloride solution, respectively, until the pH of the solution reached 7. Finally, the water and residual solvent are removed by rotary evaporation, and the collected light yellow liquid is the bromine-containing initiator monomer product.
(2)0.21g丙烯酸、0.425g多巴胺甲基丙烯酰胺、1.7292g甲氧基丙烯酸乙酯、1.08g乙氧基丙烯酸丁酯、0.05g甲基丙烯酸羟乙酯、0.07g含溴引发剂单体、0.03g偶氮二异丁腈,溶于3mLN,N-二甲基甲酰胺中,N2保护下,70℃反应12h,待反应结束后,用10mL乙酸乙酯溶解所得产物,再用400mL正己烷沉降24h,去掉上层清液,将沉降物放入60℃真空干燥箱干燥24h,得到黏附性共聚物;(2) 0.21g acrylic acid, 0.425g dopamine methacrylamide, 1.7292g ethyl methoxyacrylate, 1.08g butyl ethoxyacrylate, 0.05g hydroxyethyl methacrylate, 0.07g bromine-containing initiator monomer , 0.03g azobisisobutyronitrile, dissolved in 3mL N,N-dimethylformamide, under the protection of N2 , react at 70°C for 12h, after the reaction is over, dissolve the obtained product with 10mL ethyl acetate, and then use 400mL The n-hexane was sedimented for 24 hours, the supernatant was removed, and the sediment was placed in a 60°C vacuum drying oven to dry for 24 hours to obtain an adhesive copolymer;
(3)将上述黏附性共聚物溶于15mL二氯甲烷,将0.016g 1,6-己二异氰酸酯溶于上述溶液,得到混合物;然后将其涂覆在钛合金基板上,在烘箱中(40℃)固化24h,在钛合金表面形成交联型聚合物黏附活性层。(3) Dissolving the above-mentioned adhesive copolymer in 15 mL of dichloromethane, and dissolving 0.016 g of 1,6-hexamethylene diisocyanate in the above-mentioned solution to obtain a mixture; then coating it on a titanium alloy substrate, in an oven (40 ℃) cured for 24h to form a cross-linked polymer adhesion active layer on the surface of the titanium alloy.
(4)向12mL的试管中,依次加入6g甲基丙烯酸3-磺酸丙酯钾盐、80mg的2,2-联吡啶、35mg溴化亚铜、8mL去离子水和4mL甲醇,在氩气保护下充分搅拌均匀,配置ATRP反应液。将表面修饰了交联型聚合物黏附活性层的钛合金浸入到ATRP反应液中,在室温下反应8min,反应结束后,将其取出用纯水清洗,得到接枝了聚甲基丙烯酸3-磺酸丙酯钾聚电解质刷的亲水润滑层。(4) Into a 12 mL test tube, sequentially add 6 g of 3-sulfopropyl methacrylate potassium salt, 80 mg of 2,2-bipyridine, 35 mg of cuprous bromide, 8 mL of deionized water and 4 mL of methanol, under argon atmosphere Under the protection, stir well and evenly, configure the ATRP reaction solution. The titanium alloy with the surface-modified cross-linked polymer adhesive active layer was immersed in the ATRP reaction solution, and reacted at room temperature for 8 min. After the reaction, it was taken out and washed with pure water to obtain the grafted polymethacrylic acid 3- Hydrophilic lubricating layer of potassium propyl sulfonate polyelectrolyte brushes.
实施例2Example 2
亲水润滑涂层形貌和厚度及其与钛合金基材黏附强度的测量Measurement of Morphology and Thickness of Hydrophilic Lubricating Coating and Its Adhesion Strength to Titanium Alloy Substrate
亲水润滑涂层形貌和厚度测量:将表面修饰了润滑涂层的钛合金薄片浸没到PBS缓冲液中(pH=7.4)浸泡,待亲水润滑层溶胀平衡后将样品放入冷冻干燥机中进行脱水,而后投入液氮中进行脆断。扫描电子显微镜观测表明:实施例1中固化交联型聚合物黏附活性层表面形成聚合物-聚电解质刷复合层厚度为20μm,复合润滑层与交联型聚合物黏附底层之间结合紧密,界面没有分离现象(图2)。Measurement of the morphology and thickness of the hydrophilic lubricating coating: Immerse the titanium alloy flakes with the surface modified lubricating coating in PBS buffer (pH=7.4), and put the samples into the freeze dryer after the hydrophilic lubricating layer is swelled and equilibrated. Dehydration is carried out in liquid nitrogen, and then brittle fracture is carried out in liquid nitrogen. Scanning electron microscope observation showed that the thickness of the polymer-polyelectrolyte brush composite layer formed on the surface of the cured cross-linked polymer adhesive active layer in Example 1 was 20 μm, the composite lubricating layer and the cross-linked polymer adhesive bottom layer were tightly bonded, and the interface was There was no separation (Figure 2).
界面黏附强度测试:将实施例1中制备得到的黏附性共聚物均匀涂覆在两块钛合金中间,重叠接触面积为1cm2;待共聚物完全固化后,选用通用材料拉伸实验机(EZ-Test,SHIMADZU)对涂层在钛合金表面的黏附性能进行测试,采用平行剪切测试模式,传感器移动速度为50mm/min。实验结果如图3所示,共聚物的黏附强度为1.5MPa,说明润滑涂层和基材结合稳定。Interfacial adhesion strength test: The adhesive copolymer prepared in Example 1 was evenly coated in the middle of two titanium alloys, and the overlapping contact area was 1 cm 2 ; after the copolymer was completely cured, a general-purpose material tensile testing machine (EZ -Test, SHIMADZU) to test the adhesion performance of the coating on the surface of titanium alloy, using the parallel shear test mode, the sensor moving speed is 50mm/min. The experimental results are shown in Figure 3. The adhesion strength of the copolymer is 1.5 MPa, indicating that the lubricating coating and the substrate are combined stably.
实施例3Example 3
亲水润滑涂层力学性能测试Mechanical Properties Test of Hydrophilic Lubricating Coatings
以实施例1中制备得到的亲水润滑涂层为测试对象,选用通用材料拉伸实验机(EZ-Test,SHIMADZU)对涂层的力学性能进行测试,选用拉伸模式,传感器移动速度为50mm/min,经测量上述涂层的拉伸模量为10MPa。Taking the hydrophilic lubricating coating prepared in Example 1 as the test object, a general-purpose material tensile testing machine (EZ-Test, SHIMADZU) was used to test the mechanical properties of the coating, and the tensile mode was selected, and the sensor moving speed was 50 mm. /min, the tensile modulus of the above coating was measured to be 10 MPa.
实施例4Example 4
钛合金表面修饰了亲水润滑涂层后的摩擦学性能表征Characterization of Tribological Properties of Titanium Alloy Surface Modified with Hydrophilic Lubricating Coating
采用CSM通用摩擦磨损试验机表征涂层水润滑性能。润滑剂为水,载荷为10N,摩擦对偶为PDMS球(半径6mm),滑动速度为1Hz,共循环测试800次。实验结果如图4所示,钛合金表面修饰了亲水润滑涂层(交联型共聚物活性层+聚甲基丙烯酸3-磺酸丙酯钾聚电解质刷-共聚物复合层)后摩擦系数约为0.02;润滑涂层抗磨性能较好,800个循环测试过程中水润滑性能均较为稳定,说明本发明制备的亲水润滑涂层减摩和抗磨性能优异。The water-lubricating properties of the coatings were characterized by CSM universal friction and wear testing machine. The lubricant is water, the load is 10N, the friction pair is PDMS ball (radius 6mm), the sliding speed is 1Hz, and a total of 800 cycles are tested. The experimental results are shown in Figure 4. The friction coefficient after the titanium alloy surface is modified with a hydrophilic lubricating coating (cross-linked copolymer active layer + poly(3-propyl methacrylate) potassium polyelectrolyte brush-copolymer composite layer) about 0.02; the anti-wear performance of the lubricating coating is good, and the water-lubricating performance is relatively stable during the 800-cycle test, indicating that the hydrophilic lubricating coating prepared by the present invention has excellent anti-friction and anti-wear performance.
实施例5Example 5
钛合金表面亲水润滑涂层的抗溶胀和介质稳定性评价Evaluation of anti-swelling and medium stability of hydrophilic lubricating coatings on titanium alloys
将表面修饰了亲水润滑涂层的钛合金基材分别浸没到去、PBS缓冲液和生理盐水中,观察涂层的溶胀和结构完整性。如图5所示,与浸泡前样品相比(初始态),在3种介质中浸泡82天后,润滑涂层结构完整,与基材结合表面结合仍然紧密,无显著溶胀现象发生,说明本发明制备的亲水润滑涂层具有很好的抗溶胀和介质稳定性。The titanium alloy substrates modified with hydrophilic lubricating coatings were immersed in GO, PBS buffer and normal saline, respectively, and the swelling and structural integrity of the coatings were observed. As shown in Figure 5, compared with the sample before soaking (initial state), after soaking in three media for 82 days, the structure of the lubricating coating is complete, and the bonding surface of the substrate is still tightly combined, and no significant swelling occurs, indicating the present invention The prepared hydrophilic lubricating coating has good anti-swelling and medium stability.
实施例6Example 6
在多种基材表面修饰亲水润滑涂层Surface modification of hydrophilic lubricating coatings on various substrates
(1)0.21g丙烯酸、0.425g多巴胺甲基丙烯酰胺、2.0142g甲氧基丙烯酸乙酯、0.78g乙氧基丙烯酸丁酯、0.25g甲基丙烯酸羟乙酯、0.08g含溴引发剂单体(采用实施例1)、0.03g偶氮二异丁腈,溶于3mLN,N-二甲基甲酰胺中,N2保护下,70℃反应12h,待反应结束后,用10mL乙酸乙酯溶解所得产物,再用400mL正己烷沉降24h,去掉上层清液,将沉降物放入60℃真空干燥箱干燥24h,得到黏附性共聚物;(1) 0.21g acrylic acid, 0.425g dopamine methacrylamide, 2.0142g ethyl methoxyacrylate, 0.78g butyl ethoxyacrylate, 0.25g hydroxyethyl methacrylate, 0.08g bromine-containing initiator monomer (Example 1), 0.03g of azobisisobutyronitrile, dissolved in 3mL of N,N-dimethylformamide, under the protection of N2, reacted at 70 ° C for 12h, after the reaction was over, dissolved in 10mL of ethyl acetate to obtain the The product was then sedimented with 400 mL of n-hexane for 24 hours, the supernatant was removed, and the sediment was placed in a 60°C vacuum drying oven to dry for 24 hours to obtain an adhesive copolymer;
(3)将上述黏附性共聚物溶于15mL二氯甲烷,将0.032g 1,6-己二异氰酸酯溶于上述溶液,得到混合物;然后将其涂覆在不同类型基材表面,在烘箱中(40℃)固化24h,即可在基材表面形成交联型聚合物黏附活性层。(3) the above-mentioned adhesive copolymer was dissolved in 15 mL of dichloromethane, and 0.032 g of 1,6-hexamethylene diisocyanate was dissolved in the above-mentioned solution to obtain a mixture; then it was coated on the surface of different types of substrates, and in an oven ( 40 ℃) curing for 24h, the cross-linked polymer adhesive active layer can be formed on the surface of the substrate.
(4)向12mL的试管中,依次加入4.2g磺基甜菜碱甲基丙烯酸酯、66mg的2,2-联吡啶、30mg溴化亚铜、9mL去离子水和3mL甲醇,在氩气保护下充分搅拌均匀,配置ATRP反应液。将表面修饰了交联型聚合物黏附活性层的基材浸入到ATRP反应液中,在室温下反应15min,反应结束后,将其取出用纯水清洗,得到接枝了聚磺基甜菜碱甲基丙烯酸酯聚电解质刷的亲水润滑层。(4) Into a 12mL test tube, sequentially add 4.2g sulfobetaine methacrylate, 66mg 2,2-bipyridine, 30mg cuprous bromide, 9mL deionized water and 3mL methanol, under argon protection Fully stir and evenly prepare the ATRP reaction solution. The substrate with the surface-modified cross-linked polymer adhesive active layer was immersed in the ATRP reaction solution, and reacted at room temperature for 15 min. After the reaction, it was taken out and washed with pure water to obtain the grafted polysulfobetaine methyl. Hydrophilic lubricating layer for acrylate-based polyelectrolyte brushes.
实施例7Example 7
多种基材表面修饰了亲水润滑涂层后的摩擦学性能表征Characterization of Tribological Properties of Various Substrate Surfaces Modified with Hydrophilic Lubricating Coatings
采用CSM通用摩擦磨损试验机表征涂层水润滑性能。润滑剂为水,载荷为10N,摩擦对偶为PDMS球(半径6mm),滑动速度为1Hz,共循环测试800次。实验结果如图6所示,几种基材表面修饰了亲水润滑涂层(交联型共聚物活性层+聚磺基甜菜碱甲基丙烯酸酯聚电解质刷-共聚物复合层)后摩擦系数均小于0.04;其中,改性聚乙烯(PE)表面摩擦系数为0.013,改性钛片(Ti)表面摩擦系数为0.022,改性聚四氟乙烯(PTFE)表面摩擦系数为0.023,改性钢块表面摩擦系数为0.027,改性铝块(Al)表面摩擦系数为0.03,改性铜板表面摩擦系数为0.035;上述实验结果表明本修饰方法可以用于不同种类材料表面的亲水润滑改性。The water-lubricating properties of the coatings were characterized by CSM universal friction and wear testing machine. The lubricant is water, the load is 10N, the friction pair is PDMS ball (radius 6mm), the sliding speed is 1Hz, and a total of 800 cycles are tested. The experimental results are shown in Figure 6. The coefficient of friction after the surface of several substrates is modified with a hydrophilic lubricating coating (cross-linked copolymer active layer + polysulfobetaine methacrylate polyelectrolyte brush-copolymer composite layer) are less than 0.04; among them, the surface friction coefficient of modified polyethylene (PE) is 0.013, the surface friction coefficient of modified titanium sheet (Ti) is 0.022, the surface friction coefficient of modified polytetrafluoroethylene (PTFE) is 0.023, and the surface friction coefficient of modified steel is 0.023. The friction coefficient of the block surface is 0.027, the friction coefficient of the modified aluminum block (Al) surface is 0.03, and the surface friction coefficient of the modified copper plate is 0.035. The above experimental results show that this modification method can be used for the hydrophilic lubrication modification of different kinds of materials.
实施例8Example 8
在医疗器械表面的涂覆修饰验证Validation of Coating Finishes on Medical Device Surfaces
(1)12.33g甲基丙烯酸羟丁酯和4.10g三乙胺溶于30mL二氯甲烷中,待完全溶解后转移至250mL圆底烧瓶中,0℃冰浴中通氮气20min;23.21g溴代异丁酰溴溶于10mL二氯甲烷中,使用恒压漏斗将其逐滴加入圆底烧瓶中;在0℃冰浴环境下搅拌反应4小时后,将反应物过滤除去白色沉淀,并使用二氯甲烷清洗两次;收集滤液,依次使用饱和碳酸钠和饱和氯化钠溶液分别洗涤滤液2次,直至溶液pH达到7。最后通过旋蒸去除水分和残余溶剂,收集到浅黄色液体即为含溴引发剂单体产物。(1) 12.33g of hydroxybutyl methacrylate and 4.10g of triethylamine were dissolved in 30mL of dichloromethane, transferred to a 250mL round-bottomed flask after complete dissolution, and nitrogen was passed through an ice bath at 0°C for 20min; 23.21g of bromo Isobutyryl bromide was dissolved in 10 mL of dichloromethane, and it was added dropwise to a round-bottomed flask using a constant pressure funnel; after stirring the reaction for 4 hours in an ice bath at 0 °C, the reactant was filtered to remove the white precipitate, and di Chloromethane was washed twice; the filtrate was collected, and the filtrate was washed twice with saturated sodium carbonate and saturated sodium chloride solution, respectively, until the pH of the solution reached 7. Finally, the water and residual solvent are removed by rotary evaporation, and the collected light yellow liquid is the bromine-containing initiator monomer product.
(2)0.55g丙烯酸、1.215g多巴胺甲基丙烯酰胺、2.248g甲氧基丙烯酸乙酯、3.22g乙氧基丙烯酸丁酯、0.15g甲基丙烯酸羟乙酯、0.18g含溴引发剂单体、0.08g偶氮二异丁腈,溶于10mLN,N-二甲基甲酰胺中,N2保护下,70℃反应12h,待反应结束后,用35mL乙酸乙酯溶解所得产物,再用1000mL正己烷分三次沉降24h,去掉上层清液,将沉降物放入60℃真空干燥箱干燥24h,得到黏附性共聚物;(2) 0.55g acrylic acid, 1.215g dopamine methacrylamide, 2.248g ethyl methoxyacrylate, 3.22g butyl ethoxyacrylate, 0.15g hydroxyethyl methacrylate, 0.18g bromine-containing initiator monomer , 0.08g azobisisobutyronitrile, dissolved in 10mL N,N-dimethylformamide, under N2 protection, react at 70°C for 12h, after the reaction is over, dissolve the obtained product with 35mL ethyl acetate, and then use 1000mL n-hexane The alkane was precipitated three times for 24 hours, the supernatant liquid was removed, and the sediment was placed in a vacuum drying oven at 60 °C for 24 hours to obtain an adhesive copolymer;
(3)将上述黏附性共聚物溶于15mL二氯甲烷中,将0.016g 1,6-己二异氰酸酯溶于上述溶液,得到混合物;分别选用PVC导尿管、口腔气道插管和钛合金人工关节头作为待修饰器械,采用浸涂方式将黏附性共聚物涂覆在器械外表面,在烘箱中(60℃)固化12h,即可在三种医疗器械表面形成交联型聚合物黏附活性层。(3) above-mentioned adhesive copolymer is dissolved in 15mL of methylene chloride, and 0.016g of 1,6-hexamethylene diisocyanate is dissolved in above-mentioned solution to obtain mixture; The artificial joint head is used as a device to be modified. The adhesive copolymer is coated on the outer surface of the device by dip coating, and cured in an oven (60°C) for 12 hours, and then the cross-linked polymer adhesive activity can be formed on the surface of the three medical devices. Floor.
(4)向50mL的圆底烧瓶中,依次加入16g 2-甲基丙烯酰氧乙基磷脂酰胆碱、220mg的2,2-联吡啶、90mg溴化亚铜、20mL去离子水和12mL甲醇,在氩气保护下充分搅拌均匀,配置ATRP反应液。将表面修饰了交联型聚合物黏附活性层的三种器械浸入到ATRP反应液中,在室温下反应10min;反应结束后,将器械分别取出用纯水清洗,得到接枝了聚2-甲基丙烯酰氧乙基磷脂酰胆碱聚电解质刷的亲水润滑层。如图7所示,采用本方法可成功在三种医疗器械表面修饰亲水润滑涂层(交联型共聚物活性层+聚2-甲基丙烯酰氧乙基磷脂酰胆碱聚电解质刷-共聚物复合层),所修饰的涂层外观均匀,表明此方法在医疗器械领域的潜在应用价值。(4) Into a 50 mL round-bottomed flask, add 16 g of 2-methacryloyloxyethyl phosphatidyl choline, 220 mg of 2,2-bipyridine, 90 mg of cuprous bromide, 20 mL of deionized water and 12 mL of methanol in sequence , fully stirred under the protection of argon, and configured the ATRP reaction solution. The three kinds of devices with surface modified cross-linked polymer adhesive active layer were immersed in the ATRP reaction solution and reacted at room temperature for 10 min; after the reaction, the devices were taken out and washed with pure water to obtain the grafted poly-2-methyl methacrylate. Hydrophilic lubricating layer of acryloyloxyethylphosphatidylcholine polyelectrolyte brushes. As shown in Figure 7, the hydrophilic lubricating coating (cross-linked copolymer active layer + poly-2-methacryloyloxyethyl phosphatidylcholine polyelectrolyte brush- Copolymer composite layer), the modified coating has a uniform appearance, indicating the potential application value of this method in the field of medical devices.
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210164285.7A CN115006606B (en) | 2022-02-23 | 2022-02-23 | A kind of hydrophilic lubricating coating and its preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210164285.7A CN115006606B (en) | 2022-02-23 | 2022-02-23 | A kind of hydrophilic lubricating coating and its preparation method and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115006606A true CN115006606A (en) | 2022-09-06 |
CN115006606B CN115006606B (en) | 2023-02-24 |
Family
ID=83067724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210164285.7A Active CN115006606B (en) | 2022-02-23 | 2022-02-23 | A kind of hydrophilic lubricating coating and its preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115006606B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115747938A (en) * | 2022-11-10 | 2023-03-07 | 烟台中科先进材料与绿色化工产业技术研究院 | A multi-phase composite friction system with cross-wetting state and its construction method |
CN115814172A (en) * | 2022-12-01 | 2023-03-21 | 中山大学 | Anti-pollution wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170214047A1 (en) * | 2014-03-31 | 2017-07-27 | National Institute For Materials Science | Nano-coating material, method for manufacturing same, coating agent, functional material, and method for manufacturing same |
US20180298249A1 (en) * | 2015-06-30 | 2018-10-18 | Purdue Research Foundation | Adhesives and methods of making the same |
CN109943264A (en) * | 2019-03-08 | 2019-06-28 | 中国科学院兰州化学物理研究所 | A kind of high-strength wet adhesion biomimetic rubber material and method and application thereof |
CN110804201A (en) * | 2019-11-18 | 2020-02-18 | 中国科学院兰州化学物理研究所 | Hydrogel lubrication catheter and preparation method thereof |
CN113736011A (en) * | 2021-09-28 | 2021-12-03 | 中国科学院兰州化学物理研究所 | Hydrophobic moisture-resistant coating and preparation method and application thereof |
CN113842507A (en) * | 2021-07-19 | 2021-12-28 | 浙江大学 | Polyelectrolyte hydrogel coating with super-strong substrate adhesion performance and preparation method thereof |
-
2022
- 2022-02-23 CN CN202210164285.7A patent/CN115006606B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170214047A1 (en) * | 2014-03-31 | 2017-07-27 | National Institute For Materials Science | Nano-coating material, method for manufacturing same, coating agent, functional material, and method for manufacturing same |
US20180298249A1 (en) * | 2015-06-30 | 2018-10-18 | Purdue Research Foundation | Adhesives and methods of making the same |
CN109943264A (en) * | 2019-03-08 | 2019-06-28 | 中国科学院兰州化学物理研究所 | A kind of high-strength wet adhesion biomimetic rubber material and method and application thereof |
CN110804201A (en) * | 2019-11-18 | 2020-02-18 | 中国科学院兰州化学物理研究所 | Hydrogel lubrication catheter and preparation method thereof |
CN113842507A (en) * | 2021-07-19 | 2021-12-28 | 浙江大学 | Polyelectrolyte hydrogel coating with super-strong substrate adhesion performance and preparation method thereof |
CN113736011A (en) * | 2021-09-28 | 2021-12-03 | 中国科学院兰州化学物理研究所 | Hydrophobic moisture-resistant coating and preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
PAULGLASS, ET AL: "Enhanced Reversible Adhesion of Dopamine Methacrylamide-Coated Elastomer Microfibrillar Structures under Wet Conditions", 《LANGMUIR》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115747938A (en) * | 2022-11-10 | 2023-03-07 | 烟台中科先进材料与绿色化工产业技术研究院 | A multi-phase composite friction system with cross-wetting state and its construction method |
CN115814172A (en) * | 2022-12-01 | 2023-03-21 | 中山大学 | Anti-pollution wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof |
CN115814172B (en) * | 2022-12-01 | 2024-02-23 | 中山大学 | Anti-fouling wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN115006606B (en) | 2023-02-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9539371B2 (en) | Coating agents and coated articles | |
CN114031714B (en) | Method for modifying hydrogel lubricating coating on surface of universal equipment and universal equipment modified with hydrogel lubricating coating | |
CN115006606B (en) | A kind of hydrophilic lubricating coating and its preparation method and application | |
WO2015137259A1 (en) | Method for producing medical tool and medical tool | |
CN1202185C (en) | Hydrophilic lubricating coating layer used for medical apparatus and its coating method | |
EP1615677A2 (en) | Coating for biomedical devices | |
WO2023216874A1 (en) | Surface grafted cross-linked zwitterionic polymer coating, preparation method therefor, and use thereof | |
CN111097072A (en) | Preparation method of strong interfacial bonding hydrophilic lubricating coating on the surface of polymer medical products | |
Song et al. | High-density zwitterionic polymer brushes exhibit robust lubrication properties and high antithrombotic efficacy in blood-contacting medical devices | |
Yang et al. | Mechanically durable antibacterial nanocoatings based on zwitterionic copolymers containing dopamine segments | |
CN115814172B (en) | Anti-fouling wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof | |
EP3723839B1 (en) | Polyurea copolymer coating compositions and methods | |
Zhang et al. | A hyperbranched polymer-based water-resistant adhesive: Durable underwater adhesion and primer for anchoring anti-fouling hydrogel coating | |
CN117210040A (en) | High-adhesion high-moisture-retention slide coating, preparation method thereof and coating adhesion testing method | |
CN110204650B (en) | Anticoagulant, antibacterial, anti-adhesion, anti-inflammatory, lubricating copolymer coating material for the surface of silicone rubber material and preparation method thereof | |
JP2022520646A (en) | Biocompatible polymer coating containing therapeutic agents | |
JP2025087670A (en) | UV curable coating for medical devices | |
CN118873754A (en) | A hydrophilic anti-protein adhesion hydrogel coating for medical catheters and its preparation method and application | |
WO2023074543A1 (en) | Elongated medical instrument and method for producing same | |
Cao et al. | Poly (sulfobetaine) versus poly (ethylene glycol) based copolymer modified polyurethane catheters for antifouling | |
JPWO2020004385A1 (en) | Hydrophilic copolymers and medical devices | |
JPH07289630A (en) | Antithrombotic coating material and medical and sanitary supplies coated with the same | |
CN114652904A (en) | Anticoagulant zwitterionic hydrogel coating and preparation method thereof | |
WO2023190383A1 (en) | Polymer composition | |
JP6828876B2 (en) | Radial polymers and their design methods |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |